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研究生:黃雅凰
研究生(外文):Ya-Huang Huang
論文名稱:含對位性聚苯乙烯衍生物之立體規則性雙嵌段共聚高分子:合成方法與奈米結構自我組裝研究
論文名稱(外文):Stereoregular Diblock Copolymers of Syndiotactic Polystyrene Derivatives:Syntheses and Self-Assembled Nanostructures
指導教授:蔡敬誠
指導教授(外文):Jing-Cherng Tsai
口試委員:蔡敬誠陳信龍何榮銘林慶炫蔣酉旺
口試委員(外文):Jing-Cherng TsaiHsin-Lung ChenRong-Ming HoChing-Hsuan LinYeo-Wan Chiang
口試日期:2012-07-18
學位類別:碩士
校院名稱:國立中正大學
系所名稱:化學工程研究所
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2012
畢業學年度:100
語文別:中文
論文頁數:136
外文關鍵詞:Stereoregular Diblock CopolymersSelf-Assembled
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本研究中將苯乙烯對位位置帶有Halides官能基的單體(4-Bromostyrene,4-BrS),使用鎳金屬觸媒系統,誘導4-溴苯乙烯(4-Bromostyrene,4-BrS)單體與異丁基格氏試劑 (Isobutylmagnesium bromide)在鎳金屬觸媒催化下進行Kumada交叉耦聯反應 (Kumada cross-coupling reaction),合成出新型對位位置具備立體障礙大的苯乙烯衍生物單體((4-isobutyl)styrene, (4-iBu)S)。
所合成之單體(4-iBu)S可使用金屬茂觸媒系統Cp*Ti(OMe)3/MAO,進行對位性選擇聚合反應以合成對位異丁基苯乙烯聚合物(Syndiotactic poly(4-isobutyl)styrene,sP(4-iBu)S),藉由加入二甲基苯基乙烯基矽烷(dimethylphenylvinylsilane)作為鏈轉移劑則可生成末端具備二甲基苯基乙烯機矽烷之sP(4-iBu)S聚合物,經由去矽基、末端雙鍵氫硼化-氧化反應可有效得到末端具有氫氧 基的對位性聚對異丁基苯乙烯(hydroxyl-capped sP(4-iBu)S,sP(4-iBu)S-OH)。
本研究中還利用AlEt3作為co-initiator將sP(4-iBu)S-OH末端轉換成sP(4-iBu)S-OAlEt2之macroinitiator以進行環酯類單L-lactide的開環聚合反應,以合成出sP(4-iBu)S-b-PLLA之嵌段共聚高分子。最後我們可有效控制具有立體規則性的嵌段共聚高分子的比例並確定其結構,並藉由核磁共振儀(NMR)、小角度X光散射儀(small angle X-ray scattering)及穿透式電子顯微鏡(TEM)的分析下,我們可以確定嵌段高分子的結構及觀察其微觀相分離行為。

In this study, the original styrene structure can also be transfered to the isobutyl compounds by coupling 4-bromostyrene with isobutyl- magnesium bromide via the Nickel-catalyst-mediated Kumada coupling reaction. After that, 4-isobutylstyrene can be used as the monomers to undergo the syndiospecific polymerization.
The hydroxyl-capped sP(4-iBu)S was prepared from the hydro- boration of ethenyl-capped sP(4-iBu)S. The ethenyl-capped sP(4-iBu)S was generated by the desilylation of dimethylphenylvinylsilane-capped sP(4-iBu)S prepared via a unique vinylsilane-inducing selective chain transfer reaction during the syndiospecific polymerization of 4-isobutylstyrene conducted in the presence of dimethylphenyl- vinylsilane using Cp*Ti(OMe)3/MAO as catalyst.
We also demonstrated that the hydroxyl end-group of the sP(4-iBu)S-OH can be used to undergo living ring opening polymerization of D,L-lactide; thus, novel stereoregular diblock copolymers, including sP(4-iBu)S-b-PLLA, can be successfully prepared with high yield. Our studies clearly demonstrated that using the sP(4-iBu)S-OH as the macroinitiator for conducting living postpolymerization can lead to the successful preparations of novel stereoregular diblock copolymers, which do not require the tedious fractionation processes for removing homopolymers.
The stereoregular diblock copolymers possess precise chemical architectures (defining chemical structures with narrow ranges of molecular weight distribution) and can be self-organize into consistent nanostructures which can be proved through by small angle X-ray scattering studies.

目錄
中文摘要 I
Abstract III
目錄 V
圖目錄 IX
表目錄 XIV
第一章 緒論 1
1-1前言1-7 1
1-2烯烴的配位聚合反應的介紹 3
1-3原理介紹及文獻回顧 5
1-3-1 Kumada耦合反應簡介─鎳金屬觸媒催化8-11 5
1-3-2有機金屬茂 (metallocene)觸媒系統簡介─緣起與發展 9
1-3-3助觸媒(MAO)簡介 11
1-3-3-1助觸媒MAO在metallocene觸媒中提升活性的機制 13
1-3-3-2 metallocene觸媒的聚合反應機制 15
1-4對位聚苯乙烯高分子(Syndiotactic polystyrene,sPS)介紹 20
1-4-1聚苯乙烯的背景介紹 20
1-4-2對位性聚苯乙烯之主要物性特徵及其應用 23
1-5鏈轉移反應用於Metallocene觸媒系統合成聚烯烴12-21 24
1-6團聯共聚物(Bolck copolymers)之簡介22-28 29
1-6-1團聯共聚物之合成 29
1-6-2團聯共聚合物之微相分離型態研究29 31
1-6-3立體規則性團聯共聚物合成與自組裝行為之研究30-33 33
1-7開環聚合反應(ROP, Ring Opening Polymerization)簡介34-39 36
1-8研究動機及研究方向 40
第二章 實驗部份 42
2-1 實驗藥品 42
2-2單體與溶劑之純化40 47
2-3、實驗設備與分析儀器 49
2-3-1實驗設備 49
2-3-2分析儀器原理 51
2-4實驗步驟 59
2-4-1 4-異丁基苯乙烯((4-iBu)S)新單體合成 59
2-4-2有機茂金屬觸媒與助觸媒的配置 61
2-4-3合成末端為DMPVS-capped sP(4-iBu)S高分子 62
2-4-4合成末端為DMPVS-capped sP(4-tBu)S高分子 63
2-4-5合成末端為DMPVS-capped sPMS高分子 64
2-4-6合成末端為ethenyl-capped sP(4-iBu)S 65
2-4-7合成末端為hydroxyl-capped sP(4-iBu)S 66
2-4-8含對位性聚苯乙烯衍生物之立體規則性雙嵌段共聚高分子(Stereoregular Diblock Copolymers of Syndiotactic Polystyrene Derivatives) 67
2-5研究微觀相分離形態的實驗方法 69
2-5-1差式掃瞄熱卡計(Differential Scanning Calorimeter, DSC) 69
2-5-2穿透式電子顯微鏡(Transmission Electron Microscopy, TEM)與小角度X光散射(Small Angle X-ray Scattering, SAXS) 70
第三章 結果與討論 71
3-1 kumada耦合反應之鎳金屬觸媒機制 71
3-1-1 Kumada耦合反應之溫度對於合成(4-iBu)S的影響 73
3-1-1-1合成(4-iBu)S之微結構探討及圖譜分析 74
3-1-2鎳金屬觸媒與格氏試劑在Kumada 耦合反應中合成新單體轉化率之研究 77
3-2選擇性鏈轉移反應機制之探討41-45 79
3-3 sP(4-iBu)S末端官能化反應之研究 87
3-3-1 DMPVS-capped sP(4-iBu)S之微結構探討及圖譜分析 88
3-3-2 ethenyl-capped sP(4-iBu)S之微結構探討及圖譜分析 92
3-3-3 hydroxyl-capped sP(4-iBu)S之微結構探討及圖譜分析 94
3-4 DMPVS-t-sP(4-tBu)S之DSC分析 98
3-5低溫單聚sP(4-iBu)S DSC分析 100
3-6以開環聚合反應(ROP)聚合sP(4-iBu)S-b-PLLA 101
3-6-1分離純化sP(4-iBu)S-b-PLLA雙嵌段高分子 102
3-6-2 sP(4-iBu)S-b-PLLA之微結構探討及圖譜分析 103
3-6-3 sP(4-iBu)S-b-PLLA雙嵌段高分子之DSC分析 109
3-6-4 sP(4-iBu)S-b-PLLA雙嵌段高分子之形態學(morphology)討論 111
第四章 結論 116
參考文獻 118


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